CN107022047A - A kind of preparation method and applications of fluorine-containing amphoteric ion polymer - Google Patents
A kind of preparation method and applications of fluorine-containing amphoteric ion polymer Download PDFInfo
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Abstract
The invention provides a kind of preparation method and applications of fluorine-containing amphoteric ion polymer, using cationic vinyl monomer, acrylic acid, Fluorine containing olefine hydrophobic monomer as raw material, in the presence of surfactants, fluoropolymer is synthesized by initiator initiation reaction.The demulsifier synthesis material total amount is 100% meter, and wherein cationic vinyl monomer is 30~55%, and acrylic acid is 35~50%, and fluorine-containing alkene monomer is 3~30%；Water soluble starter addition is the 0.1~1.0% of whole vinyl monomer gross weights；Surfactant addition is the 1~4% of total monomer weight.Above-mentioned polymer is available for the processing of oil-polluted water breaking milk and removing oil.The fluoropolymer that the present invention is provided is simple in construction, easily prepare, when the fluoropolymer prepared using the method provided by the present invention is used in oily waste water treatment, can be at low temperature, short time fast emulsion breaking de-oiling, abjection water colour is clear, and the scope of application is wide, it can be not only used for low oily waste water treatment, it can also be used to high oily waste water treatment.
Description
Technical field
The invention belongs to petroleum industry field of chemicals, specifically related to a kind of novel fluoropolymers, the polymer
Synthetic method and the polymer carry out the application of demulsification de-oiling to oil-polluted water emulsion.
Background technology
Current oil exploitation mainly uses water filling oil transportation method, the continuous progress processed with oil exploitation, oil exploitation
The waste water of generation is more and more, in order to reduce water resource waste and environmental pollution, it is necessary to handle these oily waste waters,
Cycling and reutilization.Contain crude oil, number of polymers surfactant in the waste water that oil exploitation is produced, water quality is complicated so that useless
Water oil content more and more higher, generally 1000~3000mg/L, thick-oil waste water is even as high as 4000~10000mg/L, causes stone
Oil exploitation waste water recycling difficulty is bigger.Therefore need develop efficiently can normal temperature demulsification oil-contaminated water of oil field reverse-phase emulsifier solution
The certainly problem.
Industry develops serial reverse-phase emulsifier in succession since 20th century, specifically there is cationic polymer, and nonionic gathers
Compound and amphoteric ion polymer.For example, being polymerize using unsaturated quaternary ammonium salt monomer or cation that polymeric quartenary ammonium is obtained
Polymer, nonionic polyether or polyester are prepared using oxirane and expoxy propane class monomer, and using such as acrylic acid and
Simultaneous with the amphoteric ion polymer of zwitterion group in macromolecular prepared by the monomers such as insatiable hunger quaternary ammonium salt.Using both sexes from
Sub- polymer solution is as reverse-phase emulsifier, and when solution is acidity, cation number is more, can neutralize some on oil-water interfaces
Negative electrical charge, weakens emulsion interface film-strength, reaches emulsion droplet flocculate and break emulsion.There is " anti-poly- electricity in amphoteric ion polymer solution
Solve mass effect ", i.e., with the increase of liquid small molecular salt content, polymer solubility increase belongs to preferably water-soluble oil-containing
Sewage oil displacement agent.Induce one hydrophobic monomer in amphion demulsifier simultaneously, can be flocculated with the hydrophobic organic compound in sewage
Promote demulsification.Such as CN102850480B discloses the processing of a kind of polymer and its preparation method and application and oil-polluted water
Method, using acrylic compounds, cationic monomer and esters of acrylic acid hydrophobic monomer as raw material, lives in water soluble starter and surface
Property agent and nitrogen effect under, polymerization generation oily waste water treatment agent.
Because many oil fields of China all enter the exploitation middle and later periods, secondary extraction, three extractions and pressure break, acidifying are carried out
After well stimulation, oily waste water treatment reuse is more difficult, using oily waste water treatment disclosed in above-mentioned CN102850480B
When agent is as demulsifier, low temperature fast emulsion breaking oil removal efficiency has much room for improvement.Therefore require further improvement to improve oilfield sewage
Deoiling effect.
Fluorine in fluorine-containing surfactant not only hydrophobic but also had hated oil, and fluorocarbon chain can form proper alignment on aqueous solution surface
Monomolecular film, can significantly reduce the water-oil interface tension force and film strength of oil-polluted water, can reach than common hydrocarbon surface-active
The more preferable demulsification of agent, but the fluorine-containing prices of raw materials are expensive, and synthesis perfluorinated surfactant is demulsified in practical application
Possibility is little.Therefore, appropriate fluorochemical monomer is added in synthesis of surfactant and carries out telomerization, obtains with low cost, is broken
The demulsifier that breast works well, with important application value.
The content of the invention
In order to overcome demulsifier demulsification temperature of the prior art high, the deficiency of time length, the present invention provides a kind of fluorine-containing
Amphoteric ion polymer preparation method, and the application that the compound is demulsified in deoiling treatment in oil-polluted water.The fluorine-containing both sexes from
Sub- polymer can low temperature fast emulsion breaking, the demulsification de-oiling efficiency of raising oil-polluted water as demulsifier.
To achieve these goals, the present invention provides a kind of fluorine-containing amphoteric ion polymer preparation method, it is characterised in that：
By cationic vinyl monomer, acrylic acid, fluorine-containing alkene hydrophobic monomer and surfactant, by total monomer concentration be 15~
35% aqueous solution, puts into the reaction unit with stirring, Dropping feeder and condenser, stirs, under nitrogen protection,
20~40 DEG C of temperature is controlled, water soluble starter initiation reaction, 30~60 DEG C of controlling reaction temperature, polymerization insulation 2~10 is added
Hour, reaction terminates rear vacuum distillation and removes water to obtain polymer.
It is preferred that, described cationic vinyl monomer is the 72% MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride aqueous solution.
It is preferred that, described Fluorine containing olefine hydrophobic monomer is perfluorobutyl ethylene monomer, perfluorohexyl ethylene monomer,
The monomer such as 1H, 1H, 2H- perfluor -1- decene monomers or perfluoro decyl ethene it is therein any one.
It is preferred that, described water soluble starter is sodium peroxydisulfate, ammonium persulfate, the same sodium thiosulfate of hydrogen peroxide, chlorination
The oxidation-reduction system of ferrous one or more of compositions.
It is preferred that, described surfactant is lauryl sodium sulfate, cetyl trimethylammonium bromide, polyoxy second
Alkene（20）Sorbitanmonolaureate（Tween-20）, one or more in neopelex.
According to a kind of fluorine-containing amphoteric ion polymer preparation method of the present invention, its is further：The fluoropolymer
The synthesis material total amount of thing is 100% meter, and wherein cationic vinyl monomer is 30~55%, and acrylic acid is 35~50%, fluorine-containing alkene
Hydrocarbon monomer is 3~30%；Water soluble starter addition is the 0.1~1.0% of whole vinyl monomer gross weights；Surfactant
Addition is the 1~4% of total monomer weight.
Further, it is 25~35 DEG C that described water soluble starter, which adds temperature,.
Further, described polymeric reaction temperature is 30~50 DEG C, polymerization soaking time 3~6 hours.
Further, vacuum distillation water removal is 30~50 DEG C of ethanol dewaterings 20~60 minutes, 50~70 DEG C of toluene water removals 0.5
~4 hours.
Present invention also offers the fluorine-containing amphoteric ion polymer according to made from above-mentioned preparation method.
Present invention also offers a kind of application of above-mentioned fluorine-containing amphoteric ion polymer in oily waste water treatment, including make
Contacted with the fluorine-containing amphoteric ion polymer reverse-phase emulsifier of any one described with oil-polluted water.
The application of oily waste water treatment of the present invention, wherein fluorine-containing amphoteric ion polymer reverse-phase emulsifier is quality point
Number is 2~5% aqueous solution, the oil-polluted water relative to 1L, in the demulsifier fluorine-containing amphoteric ion polymer consumption be 50~
200mg, 5000~15000mg/L of oil content of oil-polluted water, Contact Temperature are 25~45 DEG C, 10~60 minutes time.
, can be short at low temperature when fluorine-containing amphoteric ion polymer prepared by the inventive method is used in oily waste water treatment
Time fast emulsion breaking de-oiling, abjection water colour is clear, and the scope of application is wide, can be not only used for low oily waste water treatment, it can also be used to Gao Han
Oily sewage disposal.
Brief description of the drawings
Fig. 1 is the hydrogen nuclear magnetic resonance spectrogram of the subject polymer of embodiment 1.
Fig. 2 is the hydrogen nuclear magnetic resonance spectrogram of the subject polymer of embodiment 2.
Fig. 3 is the hydrogen nuclear magnetic resonance spectrogram of the subject polymer of embodiment 3.
Fig. 4 is the hydrogen nuclear magnetic resonance spectrogram of the subject polymer of embodiment 4.
Fig. 5 is the hydrogen nuclear magnetic resonance spectrogram of the subject polymer of embodiment 5.
Fig. 6 is the hydrogen nuclear magnetic resonance spectrogram of the subject polymer of embodiment 6.
Embodiment
Embodiment 1
Weigh 0.5 gram of cetyl trimethylammonium bromide, 2.0 grams of perfluorohexyl ethylenes, 19.6 gram of 72% methylacryoyloxyethyl
Trimethyl ammonia chloride aqueous ammonium, 3.6 grams of acrylic acid and 50 grams of deionized waters, add and are stirred in reaction unit, nitrogen protection
Under, 30 DEG C are warming up to, 3.3 grams of aqueous solution containing 0.04 gram of hypo are added, 3.3 grams containing 0.135 gram of 30% peroxide
Change the aqueous solution of hydrogen and 0.085 gram of sodium peroxydisulfate, start reaction, then 22.8% propylene sour water is added dropwise in constant pressure separatory funnel
32.4 grams of solution, time control was dripped off at 30 minutes or so, subsequent reactions 3 hours.45 DEG C of vacuum distillation ethanol dewatering 40 minutes,
65 DEG C of toluene remove water 60 minutes to obtain light yellow solid, i.e. fluoropolymer oil-polluted water demulsifier.
The proton nmr spectra (dimethyl sulfoxide (DMSO)-d6 makees solvent) of embodiment 1 is as shown in figure 1, displacement 1.24 and 0.86
Locate as CH in cetyl trimethylammonium bromide3-（CH2）13- proton peak, 1.06 be-CH in residual solvent ethanol3Proton peak,
1.91 be-C (CH in MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride3)-(CO)-in-CH3Proton peak, 3.28 be water peak, 3.43
For in MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride with-N+Connected-CH3Proton peak, is-N at 4.28 and 4.53+Connected
Two methylene-CH2- proton peak, and the multiplet between 5.76~6.34, then be the end group CH of each monomer2=CH2After-polymerization
Proton peak, wherein 5.76 and 6.12 be-CH after the polymerization of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride end alkene2- proton peak, 5.93
It is end-the CH of perfluorohexyl ethylene with 5.962- CH- proton peaks.6.09~6.34 be-CH after acroleic acid polymerization2-CH2- proton
Peak.
Above test result shows to have synthesized target fluoro polymer.
Embodiment 2
Weigh 0.59 gram of cetyl trimethylammonium bromide, 3.0 grams of perfluorohexyl ethylenes, 16.6 gram of 72% methacryloxypropyl second
Base trimethyl ammonia chloride aqueous ammonium, 4.15 grams of acrylic acid and 50 grams of deionized waters, are added and are stirred in reaction unit, and nitrogen is protected
Under shield, 30 DEG C are warming up to, 3.3 grams of aqueous solution containing 0.04 gram of hypo are added, 3.3 grams containing 0.135 gram of 30% mistake
The aqueous solution of hydrogen oxide and 0.085 gram of sodium peroxydisulfate, starts reaction, then 25% propylene sour water is added dropwise in constant pressure separatory funnel
33.4 grams of solution, time control was dripped off at 30 minutes or so, subsequent reactions 4 hours.45 DEG C of vacuum distillation ethanol dewatering 20 minutes,
65 DEG C of toluene remove water 60 minutes to obtain light yellow solid, i.e. fluoropolymer oil-polluted water demulsifier.
The proton nmr spectra (dimethyl sulfoxide (DMSO)-d6 makees solvent) of embodiment 2 is analyzed as shown in Fig. 2 the He of displacement 1.24
It is CH in cetyl trimethylammonium bromide at 0.853-（CH2）13- proton peak, 1.06 be residual solvent ethanol-CH3Proton peak,
1.91 be-C (CH in MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride3)-(CO)-in-CH3Proton peak, 3.28 be water peak, 3.45
For in MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride with-N+Connected-CH3Proton peak, is-N at 4.28 and 4.53+Connected
Two methylene-CH2- proton peak, and the multiplet between 5.76~6.34, then be the end group CH of each monomer2Matter after=CH- polymerizations
Sub- peak, wherein 5.76 and 6.13 be-CH after the polymerization of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride end alkene2- CH- proton peaks,
5.93 and 5.96 be the end-CH of perfluorohexyl ethylene2- CH- proton peaks.6.09~6.34 be-CH after acroleic acid polymerization2- CH- matter
Sub- peak.
Above test result shows to have synthesized target fluoro polymer.
Embodiment 3
Weigh 0.7 gram of cetyl trimethylammonium bromide, 5.0 grams of perfluorohexyl ethylenes, 16.6 gram of 72% methylacryoyloxyethyl
Trimethyl ammonia chloride aqueous ammonium, 4.15 grams of acrylic acid and 50 grams of deionized waters, add and are stirred in reaction unit, nitrogen protection
Under, 30 DEG C are warming up to, 3.4 grams of aqueous solution containing 0.02 gram of hypo are added, 3.4 grams containing 0.07 gram of 30% peroxide
Change the aqueous solution of hydrogen and 0.04 gram of sodium peroxydisulfate, start reaction, then 25% acrylic acid aqueous solution is added dropwise in constant pressure separatory funnel
33.4 grams, time control was dripped off at 30 minutes or so, subsequent reactions 3 hours.45 DEG C of vacuum distillation ethanol dewatering 30 minutes, 65 DEG C
Toluene removes water 90 minutes to obtain light yellow solid, i.e. fluoropolymer oil-polluted water demulsifier.
The proton nmr spectra (dimethyl sulfoxide (DMSO)-d6 makees solvent) of embodiment 3 is analyzed as shown in figure 3, the He of displacement 1.24
It is CH in cetyl trimethylammonium bromide at 0.853-（CH2）13- proton peak, 1.06 be residual solvent ethanol-CH3Proton peak,
1.91 be-C (CH in MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride3)-(CO)-in-CH3Proton peak, 3.28 be water peak, 3.40
For in MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride with-N+Connected-CH3Proton peak, is-N at 4.28 and 4.52+Connected
Two methylene-CH2- proton peak, and the multiplet between 5.76~6.33, then be the end group CH of each monomer2Matter after=CH- polymerizations
Sub- peak, wherein 5.76 and 6.12 be-CH after the polymerization of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride end alkene2- CH- proton peaks,
5.93 and 5.95 be the end-CH of perfluorohexyl ethylene2- CH- proton peaks.6.09~6.33 be-CH after acroleic acid polymerization2- CH- matter
Sub- peak.
Above test result shows to have synthesized target fluoro polymer.
Embodiment 4
Weigh 0.5 gram of cetyl trimethylammonium bromide, 1.0 grams of perfluorobutyl ethylenes, 16.6 gram of 72% methylacryoyloxyethyl
Trimethyl ammonia chloride aqueous ammonium, 4.15 grams of acrylic acid and 50 grams of deionized waters, add and are stirred in reaction unit, nitrogen protection
Under, 30 DEG C are warming up to, 3.3 grams of aqueous solution containing 0.04 gram of hypo are added, 3.3 grams containing 0.135 gram of 30% peroxide
Change the aqueous solution of hydrogen and 0.085 gram of sodium peroxydisulfate, start reaction, then constant pressure separatory funnel be added dropwise 25% acrylic acid it is water-soluble
33.4 grams of liquid, time control was dripped off at 30 minutes or so, subsequent reactions 5 hours.45 DEG C of vacuum distillation ethanol dewatering 40 minutes, 65
DEG C toluene removes water 40 minutes to obtain light yellow solid, i.e. fluoropolymer oil-polluted water demulsifier.
The proton nmr spectra (dimethyl sulfoxide (DMSO)-d6 makees solvent) of embodiment 4 is analyzed as shown in figure 4, the He of displacement 1.24
It is CH in cetyl trimethylammonium bromide at 0.853-（CH2）13- proton peak, 1.06 be residual solvent ethanol-CH3Proton peak,
1.91 be-C (CH in MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride3)-(CO)-in-CH3Proton peak, 3.29 be water peak, 3.45
For in MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride with-N+Connected-CH3Proton peak, is-N at 4.28 and 4.54+Connected
Two methylene-CH2- proton peak, and the multiplet between 5.76~6.34, then be the end group CH of each monomer2Matter after=CH- polymerizations
Sub- peak, wherein 5.76 and 6.13 be-CH after the polymerization of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride end alkene2- CH- proton peaks,
5.93 and 5.96 be the end-CH of perfluorohexyl ethylene2- CH- proton peaks.6.09~6.34 be-CH after acroleic acid polymerization2- CH- matter
Sub- peak.
Above test result shows to have synthesized target fluoro polymer.
Embodiment 5
Weigh 0.6 gram of cetyl trimethylammonium bromide, 10.0 grams of perfluorohexyl ethylenes, 16.6 gram of 72% methacryloxypropyl second
Base trimethyl ammonia chloride aqueous ammonium, 4.15 grams of acrylic acid and 50 grams of deionized waters, are added and are stirred in reaction unit, and nitrogen is protected
Under shield, 30 DEG C are warming up to, 3.35 grams of aqueous solution containing 0.06 gram of hypo are added, 3.35 grams contain 0.202 gram 30%
The aqueous solution of hydrogen peroxide and 0.128 gram of sodium peroxydisulfate, starts reaction, then 25% acrylic acid is added dropwise in constant pressure separatory funnel
33.4 grams of the aqueous solution, time control was dripped off at 30 minutes or so, subsequent reactions 3 hours.45 DEG C of vacuum distillation, 20 points of ethanol dewatering
Clock, 65 DEG C of toluene remove water 2 hours to obtain light yellow solid, i.e. fluoropolymer oil-polluted water demulsifier.
The proton nmr spectra (dimethyl sulfoxide (DMSO)-d6 makees solvent) of embodiment 5 is analyzed as shown in figure 5, the He of displacement 1.24
It is CH in cetyl trimethylammonium bromide at 0.853-（CH2）13- proton peak, 1.06 be residual solvent ethanol-CH3Proton peak,
1.91 be-C (CH in MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride3)-(CO)-in-CH3Proton peak, 3.28 be water peak, 3.40
For in MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride with-N+Connected-CH3Proton peak, is-N at 4.28 and 4.53+Connected
Two methylene-CH2- proton peak, and the multiplet between 5.76~6.34, then be the end group CH of each monomer2Matter after=CH- polymerizations
Sub- peak, wherein 5.76 and 6.12 be-CH after the polymerization of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride end alkene2- CH- proton peaks,
5.93 and 5.96 be the end-CH of perfluorohexyl ethylene2- CH- proton peaks.6.09~6.34 be-CH after acroleic acid polymerization2- CH- matter
Sub- peak.
Above test result shows to have synthesized target fluoro polymer.
Embodiment 6
Weigh 0.54 gram of cetyl trimethylammonium bromide, 1.0 grams of 1H, 1H, 2H- perfluor -1- decene, 16.6 gram of 72% methyl-prop
Alkene acyloxyethyl trimethyl ammonia chloride aqueous ammonium, 4.15 grams of acrylic acid and 50 grams of deionized waters, add in reaction unit and stir equal
It is even, under nitrogen protection, 30 DEG C are warming up to, 3.3 grams of aqueous solution containing 0.04 gram of hypo are added, 3.3 grams contain
The aqueous solution of 0.135 gram of 30% hydrogen peroxide and 0.085 gram of sodium peroxydisulfate, starts reaction, then constant pressure separatory funnel is added dropwise
33.4 grams of 25% acrylic acid aqueous solution, time control was dripped off at 30 minutes or so, subsequent reactions 5 hours.45 DEG C of second of vacuum distillation
Alcohol is removed water 40 minutes, and 65 DEG C of toluene remove water 60 minutes to obtain light yellow solid, i.e. fluoropolymer oil-polluted water demulsifier.
The proton nmr spectra (dimethyl sulfoxide (DMSO)-d6 makees solvent) of embodiment 6 is analyzed as shown in fig. 6, the He of displacement 0.86
It is CH in cetyl trimethylammonium bromide at 1.243-（CH2）13- proton peak, 1.06 be residual solvent ethanol-CH3Proton peak,
1.91 it is-C (CH in MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride3)-(CO)-in-CH3Proton peak, 3.27 be water peak, 3.45
For in MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride with-N+Connected-CH3Proton peak, is-N at 4.28 and 4.54+Connected
Two methylene-CH2- proton peak, and the multiplet between 5.76~6.34, then be the end group CH of each monomer2Matter after=CH- polymerizations
Sub- peak, wherein 5.76 and 6.12 be-CH after the polymerization of MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride end alkene2- CH- proton peaks,
5.93 and 5.95 be the end-CH of perfluorohexyl ethylene2- CH- proton peaks.6.09~6.34 be-CH after acroleic acid polymerization2- CH- matter
Sub- peak.
Above test result shows to have synthesized target fluoro polymer.
Embodiment 7
Weigh 0.54 gram of cetyl trimethylammonium bromide, 5.0 grams of perfluorohexyl ethylenes, 16.6 gram of 72% methacryloxypropyl second
Base trimethyl ammonia chloride aqueous ammonium, 4.15 grams of acrylic acid and 50 grams of deionized waters, are added and are stirred in reaction unit, and nitrogen is protected
Under shield, 30 DEG C are warming up to, 3.3 grams of aqueous solution containing 0.04 gram of hypo are added, 3.3 grams containing 0.085 gram of over cure
Sour potassium and 0.085 gram of azo（2- amidine propanes）The aqueous solution of dihydride, starts reaction, then constant pressure separatory funnel is added dropwise
33.4 grams of 25% acrylic acid aqueous solution, time control was dripped off at 30 minutes or so, subsequent reactions 5 hours.45 DEG C of second of vacuum distillation
Alcohol is removed water 40 minutes, and 65 DEG C of toluene remove water 60 minutes to obtain light yellow solid, i.e. fluoropolymer oil-polluted water demulsifier.
Above test result shows to have synthesized target fluoro polymer.
Proton nmr spectra (dimethyl sulfoxide (DMSO)-d6 makees solvent) be the same as Example 1 of embodiment 7.
Embodiment 8
Weigh 0.5 gram of sodium dodecyl benzenylsulfonate, 2.0 grams of perfluorohexyl ethylenes, 19.6 gram of 72% methylacryoyloxyethyl front three
The ammonium chloride aqueous solution, 3.6 grams of acrylic acid and 50 grams of deionized waters, add and are stirred in reaction unit, under nitrogen protection, rise
Temperature adds 3.3 grams of aqueous solution containing 0.04 gram of hypo, 3.3 grams containing 0.135 gram of 30% hydrogen peroxide to 30 DEG C
With the aqueous solution of 0.085 gram of sodium peroxydisulfate, start reaction, then 22.8% acrylic acid aqueous solution is added dropwise in constant pressure separatory funnel
32.4 grams, time control was dripped off at 30 minutes or so, subsequent reactions 3 hours.45 DEG C of vacuum distillation ethanol dewatering 40 minutes, 65 DEG C
Toluene removes water 60 minutes to obtain light yellow solid, i.e. fluoropolymer oil-polluted water demulsifier.
Above test result shows to have synthesized target fluoro polymer.
Proton nmr spectra (dimethyl sulfoxide (DMSO)-d6 makees solvent) be the same as Example 1 of embodiment 8.
Fluoropolymer oil-polluted water demulsifier oil separated rate evaluation experimental prepared by embodiment 1~8.
With reference to China National Petroleum professional standard SY/T5797-93《Demulsifier for oil in water emulsion performance is evaluated
Method》Oil-in-water emulsion is prepared, demulsification experiment is carried out；And with reference to China National Petroleum professional standard SY/T5329-2012
《Clastic rock reservoir water water quality index and analysis method》Aqueous phase oil-containing is observed, aqueous phase oil content is tested.
Polymer prepared by above-described embodiment 1~6 is configured to the aqueous solution that mass fraction is 4%, measures preparation and obtains
Solution ph be each about 3, the demulsifier aqueous solution is added into the oil-in-water emulsion for preparing（Measure oil content 10582mg/
L）, polymer concentration is 100mg/L in emulsion, at 30 DEG C, is reacted 0.5 hour, observes oil-water interfaces, carries out water-oil separating,
Aqueous phase oil content and de-oiling rate are tested, shown in concrete outcome table 1.
Demulsification de-oiling effect of table 1 demulsifier, 1~8 pair of oil-in-water containing fat liquor
| Demulsifier | Consumption（mg/L） | Oil-water interfaces | Water colour | Oil content in aqueous phase（mg/L） | De-oiling rate（%） |
| Embodiment 1 | 100 | Neatly | Clearly | 141.1 | 98.7 |
| Embodiment 2 | 100 | Neatly | Clearly | 148.8 | 98.6 |
| Embodiment 3 | 100 | Neatly | Clearly | 144 | 98.6 |
| Embodiment 4 | 100 | Neatly | Clearly | 151.8 | 98.6 |
| Embodiment 5 | 100 | Neatly | Clearly | 173.9 | 98.4 |
| Embodiment 6 | 100 | Neatly | Clearly | 169.1 | 98.4 |
| Embodiment 7 | 100 | Neatly | Clearly | 225.6 | 97.9 |
| Embodiment 8 | 100 | Neatly | Clearly | 182.9 | 98.3 |
| Blank | 0 | - | - | 10582 | 0 |
Test result indicates that, fluoropolymer demulsifier of the present invention is respectively provided with good demulsification de-oiling effect, de-oiling rate
For 98-99%, can low-temperature demulsification, and de-emulsification speed is fast, the clear consolidation of oil-water interfaces, the advantages of water colour is clear.
Claims (9)
1. a kind of preparation of fluorine-containing amphoteric ion polymer, it is characterised in that：, will using water as solvent using following preparation method
Cationic vinyl monomer, acrylic acid, Fluorine containing olefine hydrophobic monomer and surfactant, by total monomer add concentration for 15~
35%, it is added in the reaction unit with stirring, Dropping feeder and condenser, under nitrogen protection, controls 20~40 DEG C of temperature,
Stir.
2. water soluble starter initiation reaction is added, 30~60 DEG C of controlling reaction temperature, polymerization insulation 2~10 hours, reaction knot
Vacuum distillation removes water to obtain polymer after beam.
3. a kind of preparation of fluorine-containing amphoteric ion polymer according to claim 1, it is characterised in that：Described cation
Vinyl monomer is the 72% MethacryloyloxyethylTrimethyl Trimethyl Ammonium Chloride aqueous solution.
4. a kind of preparation of fluorine-containing amphoteric ion polymer according to claim 1, it is characterised in that：Described fluorine-containing alkene
Hydrophobic monomer is perfluorobutyl ethylene monomer, perfluorohexyl ethylene monomer, 1H, 1H, 2H- perfluor -1- decene monomers or perfluor
The monomers such as decyl ethylene one or more therein.
5. a kind of preparation of fluorine-containing amphoteric ion polymer according to claim 1, it is characterised in that：Described water solubility
Initiator is sodium peroxydisulfate, ammonium persulfate, hydrogen peroxide and sodium thiosulfate, the oxygen of one or more of compositions of frerrous chloride
Change-reduction system.
6. a kind of preparation of fluorine-containing amphoteric ion polymer according to claim 1, it is characterised in that：Live on described surface
Property agent be lauryl sodium sulfate, cetyl trimethylammonium bromide, polyoxyethylene（20）Sorbitanmonolaureate（I.e.
Tween-20）, one or more in neopelex.
7. a kind of preparation of fluorine-containing amphoteric ion polymer according to claim 1, it is characterised in that：
Described fluorine-containing amphoteric ion polymer synthesis material total amount be 100% meter, wherein cationic vinyl monomer be 30~
55%, acrylic acid is 35~50%, and fluorine-containing alkene monomer is 3~30%；Water soluble starter addition is whole vinyl monomer gross weights
The 0.1~1.0% of amount；Surfactant addition is the 1~4% of total monomer weight；Water soluble starter add temperature be 25~
35℃；Polymeric reaction temperature is 30~50 DEG C, polymerization soaking time 3~6 hours；Vacuum distillation water removal removes for 30~50 DEG C of ethanol
Water 20~60 minutes, 50~70 DEG C of toluene are removed water 0.5~4 hour.
8. a kind of preparation of fluorine-containing amphoteric ion polymer according to claim 1, it is characterised in that：It is fluorine-containing that it is prepared
Amphoteric ion polymer is applied in oily waste water treatment, anti-including the use of the fluorine-containing amphoteric ion polymer of any one described
Phase demulsifier is contacted with oil-polluted water.
9. application according to claim 7, it is characterised in that：Described fluorine-containing amphoteric ion polymer reverse-phase emulsifier is
Mass fraction is 2~5% aqueous solution, the oil-polluted water relative to 1L, fluorine-containing amphoteric ion polymer in the demulsifier, uses
Measure as 50~200mg, 5000~15000mg/L of oil content of oil-polluted water, Contact Temperature is 25~45 DEG C, 10~60 points of time
Clock.
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